Methoxide‐Enabled Zirconium‐Catalyzed Migratory Alkene Hydrosilylation

Abstract

A zirconocene dichloride‐catalyzed alkene hydrosilylation is reported that can be applied to non‐activated and conjugated terminal and internal alkenes. It involves a catalytic Zr‐walk process and leads to a selective conversion to the linear product. Lithium methoxide serves as mild catalyst activating agent, which significantly increases the applicability and operational simplicity in comparison to earlier zirconium(II)‐based protocols. Supported by additional experiments and calculations, a mechanism via zirconium(IV) intermediates is proposed. Due to the benign nature and ready‐availability of the zirconium catalyst, the reaction is an attractive alternative to established alkene hydrosilylation methods.